Biocidal quaternary ammonium aromatic cyclic imides



United States Patent Oflice 3,300,377 Patented Jan. 24, 1967 3,300,377 BIOCIDAL QUATERNARY AMMONIUM AROMATIC CYCLHC IMIDES William J. Shibe, .lr., Riverton, N.J., and Marcus Sittenfield, Philadelphia, Pa., assignors to Hollichem Corporation, Camden, N.J., a corporation of New Jersey N Drawing. Original application Jan. 16, 1962, Ser. No. 166,699, now Patent No. 3,133,072, dated May 12, 1964. Divided and this application Apr. 3, 1964, Ser. No. 357,269

2 Claims. (Cl. 167-33) This invention relates to quaternary ammonium compounds, and it particularly relates to biocidal quaternary ammonium cyclic imides. It is a divisional application of applicants copending application Serial No. 166,699, filed January 16, 1962, and now issued as US. Patent No. 3,133,072, dated May 12, 1964.

It has heretofore been found that the reaction products of various quaternary ammonium compounds and benzosulfim-ide (saccharin) were quite active biocidal agents, generally superior to ordinary quaternary ammonium compounds in this respect and, furthermore, possessed of a sweet, pleasant taste not found in ordinary quaternaries. In addition, it was found that such quaternary ammonium benzosulfirnides had inherent antistatic properties when incorporated in electrically non-conductive materials such as paper, glass, rubber, textiles, plastics and the like, and were also capable of being readily complexed with halogens to retain all the highly effective germicidal properties of the halogens while substantially eliminating their undesirable properties such as their relatively high degree of toxicity, their tendency to irriate the skin and their tendency to stain both skin and fabrics. It has also been found that certain quaternary ammonium benzosulfimides have thixotropic properties making them highly desirable thickening agents for various purposes. However, all these properties were heretofore believed limited to the quaternary ammonium benzosulfimides.

It has now been discovered that the above properties are not limited to the quaternary ammonium benzosulfimides ibut are, in addition, possessed in general by all other quaternary ammonium aromatic cyclic imides Where the aromatic nucleus has attached thereto in those positions not attached to the cyclic imide radical a member of the group consisting of hydrogen, halogen, alkyl and alkoxy, and wherein the cyclic imide radical has the formula NHCOX wherein X is a member of the group consisting of CO, O, S and N.

Illustrative of the aromatic cyclic imides utilizab'le in the present invention are:

phthalimide:

naphth alimide H N O=(]J 0 0 2,6-dichlorobenzoxazolinone:

tetrachlorophthalimide:

NH 0 ll benzothiazolinone:

s 6-methylbenzoxazolinone:

For most purposes, the quaternary ammonium radical may be selected from any of the well-known class of quaternary ammonium groups as, for example, the alkyl quaternaries such :as lauryl trimethyl ammonium, stearyl trimethyl ammonium, stearyl dimethyl ethyl ammonium, cetyl dimethyl ethyl ammonium, myristryl dimethyl ethyl ammonium, lauryl dimethyl ethyl ammonium, tallow itrimethyl ammonium, hydrogenated tallow trimethyl ammonium, coco trimethyl ammonium, di-hydrogenated tallow dimethyl ammonium, di-coco dimethyl ammonium, di-soya dimethyl ammonium, hydrogenated tallow dimethyl ethyl ammonium, coco dimethyl ethyl ammonium, tallow dimethyl ethyl ammonium and soya dimethyl et'hyl ammonium; the alkylaryl quaternaries such as lauryl dimethyl benzyl ammonium, alkyl dimethyl benzyl ammonium, cetyl dimethyl benzyl ammonium, stearyl dimethyl benzyl ammonium, alkyl dimethyl dichlorobenzyl ammonium, alkyl dimethyl ethyl benzyl ammonium, alkyl dimethyl dimethyl benzyl ammonium, dodecyl benzyl trimethyl ammonium, dodecyl methyl benzyl trimethyl ammonium, octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium, soya dimethyl benzyl ammonium, hydrogenated tallow dimethyl benzyl ammonibenzyl hydroxethyl imidazoliniuim, alkenyl ethyl benzyl hydroxyethyl imidazolinium, alkenyl diclrlorobenzyl hydroxyethyl imi'dazolinium, coco benzyl hydroxyethyl imidazoliniwm, coco ethyl hydroxyethyl imidazolinium, stearyl ethyl hydroxyethyl imidazolinium, stearyl benzyl hydroxyethyl imidazolinium, stearyl dichlorobenzyl hydroxyethyl imidazolinium :and stearyl ethyl benzyl hydroxyethyl imidazolinium; the morpholiniums such as coco methyl morpholinium and myristyl methyl morpho linium; and the N-pyrinidiniums such as N-(stearoyl colamino formyl methyD-pyridinium and N-(lauroyl colamino fonmyl methyl) pyridinium.

The quaternary ammonium aromatic cyclic imides of the above type are, as stated, generally all efiective in the manner disclosed except that only particular ones are thioxotropic and, therefore, suitable as thickening agents. These thixotropic compounds are those wherein the quaternary radical comprises four alkyl groups attached to the nitrogen atom, one of these groups being a long chain group having at least 14 carbon atoms in the chain, preferably 14-22 carbon atoms, and the other three groups being lower alkyls having no more than carbon atoms in the chain. Among the quaternaries within this scope are unyristyl trimethyl ammonium, cetyl trimethyl ammonium, stearyl trimethyl ammonium, arachidyl trimethyl ammonium, behenyl trirnethyl ammonium, myristyl dimethyl ethyl ammonium, cetyl dimethyl ethyl ammonium, stearyl dimethyl ethyl ammonium, arachidyl dimethyl ethyl ammonium, behenyl dimethyl ethyl ammonium, and the like.

The various compounds embodying the present invention are generally prepared in substantially the same manner by reacting stoichiometric amounts of a selected quaternary ammonium salt, such as a halide or sulfate, with a selected aromatic cyclic imide or with an alkali metal salt of such irnide in an aqueous solution wherein the components react with each other to form the desired product. Alternatively, an alcoholic solution may be used instead of the aqueous solution. Usually, agitation is required and the reaction may be carried out at ambient temperatures although, generally, the application of additional heat is preferable.

The following specific examples are provided for i1- lustrative purposes only and with no intent to necessarily limit the inventive scope except as claimed:

Example 1 319.5 gms. of Arquad 16-50 (produced by the Armour Chemical Division, Armour & Co., Chicago, 111.), a product containing a 50% by weight concentration of cetyl trimethyl ammonium chloride, were diluted with 320 grams of deionized water, thereby making a 25% solution of the chloride. 92.5 grams /z mol) of potassuim phthalimide were dissolved in 277 grams of deionized water. The two solutions were then blended and agitated for 5 minutes at ambient temperatures and pressure to form a clear aqueous solution. This solution was then evaporated to dryness in a forced draft oven at 212 F. The dry residue was extracted with hot 99% methanol. The alcoholic solution was then agitated and filtered and the insoluble salt removed. The filtrate was then evaporated to dryness. The residue was cetyl trimethyl ammonium phtha'limide.

Example 2 380 grams of a 50% aqueous solution of alkyl dimethyl benzyl ammonium chloride were diluted to 25% solids with 380 grams of deionized water. 98.5 grams /2 mol) of naphthalimide were dissolved in liters of deionized water containing 20- grams of sodium hydroxide. The two aqueous solutions were then mixed and heated, with agitation, to 100 C. An oily layer formed on the surface and was separated in a separatory funnel. This oily layer was then dried in a vacuum oven at F. to produce alkyl dimethyl benzyl ammonium naphthalimide as the end product.

Example 3 187.8 grams 0/: mol) of cetyl pyridinium chloride were dissolved in 1 liter of 99% isopropanol, 102 grams /2 mol) of 2,6-dichlorobenzoxazolinone were dissolved in 1 liter of 99% isopropanol. The two alcoholic solutions were then mixed together With agitation and during the agitation 20 grams of sodium hydroxide dissolved in 400 grams of ethyl alcohol were added to the mixture. The resulting solution was evaporated to 1 liter and cooled to room temperature, after which the salt sodium chloride was removed. The filtrate was then further evaporated to dryness. The residue, a dark brown, pasty solid, was cetyl pyridinium 2,6-dichlorobenzoxazolinone.

Example 4 224.25 grams /2 mol) of octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride were dissolved in 1 liter of deionized water. 161.5 grams of potassium tetrachlorophthalimide were dissolved in 5 liters of deionized water. The two aqueous solutions were then mixed and heated to 212 F. An oily layer was obtained and this oily layer was separated in a separatory funnel and then dried in a vacuum oven. The resultant residue was octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium tetrachlorophthalimide.

Example 5 68.5 grams /2 mol) of benzothiozolinone were dissolved in 1 liter of isopropanol. 359 grams of a 50% solution of dodecyl benzyl trimethyl ammonium chloride were added with agitation. 20 grams of sodium hydroxide dissolved in 400 grams of ethyl alcohol were then added with agitation. The resultant solution was then evaporated to dryness in a vacuum oven at 140 F. The resultant residue was then dissolved in 1 liter of 99% isopropanol. The resultant salt precipitated out and was removed by filtration. The filtrate was then evaporated to dryness in a vacuum oven at 140 F. The final product obtained was a brown, pasty solid identified as dodecyl benzyl trimethyl ammonium benzothiozolinone.

Example 6 233 grams (/2 mol) of lauryl isoquinolinium bromide at 75% strength was diluted to 25% strength with 466 grams or isopropanol. 99.5 grams of 6-methyl phthalimide was dissolved in 298 grams of deionized water. The alcoholic quaternary solution and the water solution of the phthalimide were then mixed and heated to 212 F. The non-aqueous layer, a brown, viscous mass, was then separated and dried in a vacuum oven. The resultant brown, pasty solid was identified as lauryl isoquinolinium 6-methyl phthalimide.

Example 7 83.5 grams 6. mol) of S-methoxy benzothiozolinone were dissolved in 1 liter of isopropanol. 192.75 grams /2 mol) of cetyl dimethyl benzyl ammonium chloride were dissolved in 1 liter of deionized water. The alooholic benzothiozolinone solution and the aqueous quaternary solution were then mixed and to the mixture was added 20 grams of sodium hydroxide. The resultant solution was evacuated to dryness in a vacuum oven at 140 F. and the solute was taken up with 1 liter of isopropanol. The resultant salt precipitated out and was removed by filtration. The filtrate was then dried in a vacuum oven at 140 F. The residue constituting the final product was a yellow powder identified as cetyl dimethyl benzyl ammonium S-methoxy benzothiozolinone.

Example 8 ionized water and this solution was then heated to 160 F. at which point 28.5 grams of iodine crystals were added with agitation until the iodine was completely dissolved. The quaternary ammonium iodine com- 6 The behenyl trimethyl ammonium phthalirnide, the Tamo-l-731, the Colloid 606, the ethylene glycol, the Titanox RA-SO the Snowflake, the A.S.P.-400 and the Celite-281 are mixed until a smooth paste is formed.

plex was then cooled to 75 F. 87.5 grams /2 mol) 5 The water is then added to achieve the desired milling of potassium plit a i e was dissolved in deionized water viscosity and the mass is passed through a suitable millto make a 10% aqueous olution and this latter solution ing machine. The carbitol, *Igepol CO-630 and polywas then added to the q aternary solution with rapid vinyl acetate are then added and thoroughly mixed into and vigorous agitation. E16 resultant complex was septhe composition. If necessary, additional water may be arated as a crystalline ss and the supernatent water 10 added to adjust the viscosity as desired. solution was decanted. *The precipitate was then further The thixotropic properties of the above type compounds washed with deionized water. The ectyl dimethyl benzyl make them ideal thickening agents not only for .paints but ammonium phthalimide-iodine complex was then filtered for lotions, creams and the like. They are also ffectively and dried under reduced pressure. used in the drilling of oil since they act to kee the clay Illustrative of the biocidal properties of the compounds in suspension and prevent its settling out, thereby keeping of the present invention, bacteriostatic tests involving the the clay fluid and preventing clogging. They also are following minimum concentnations of representative comeffective thickeners for pumping mixtures which are used pounds gave halos of at least 1 in agar plate to carry up the drilling refuse and simultaneously act as studies: biocides against algae and the like, thereby reducing the Staphylo- Staph. our. Compound coccus aurcus E. coli, E. typhosi, Antibiotic- 209, percent percent percent resistant str., percent Alkyl dimethyl benzyl ammonium bcnzosulfimide 0. 01 0.1 0. 1 0. 01 Alkyl dimethyl beiizyl ammonium phthalimide 0. 01 0. 1 0. 1 0. 01 Alkyl dimethyl benzyl ammonium naphthalimide 0. 01 0. 1 0. 1 0. 01 Alkyl dimethyl benzyl ammonium 2,6-dichloiobenzoxa nlinnne 0.01 0.1 0.1 0. 01 Alkyl dimethyl benzyl ammonium tetrachlorophthalimide 0. 01 0. 1 0. 1 0. 01 Alkyl dimethyl benzyl ammonium benzothiozolinone 0. 01 0.1 0.1 0. 01 Alky] dimethyl benzyl ammonium phthalimidebromine (10% bromine) 0.006 0. 06 0.006

The above compounds within the scope of the present slime. They also act to automatically seal up leaks and invention having quaternary radicals comprising four fissures in the substrata. alkyl groups attached to the nitrogen atom, wherein one Quaternary ammonium aromatic cyclic imides of the alkyl group is a long chain of at least 14 carbon atoms type contemplated herein are also very effective antiand the other three are lower alkyls of 1 to 5 carbon static agents when physically combined with electrically atoms, have very effective thixotropic properties. These non-conductive substances such as paper, textiles, skins, properties are retained and may even be enhanced in leathers, furs, plastics, etc. They may be incorporated the presence of alkali metal, ammonium or alkaline earth in waxes and polishes for furniture, automobiles, floors, salts. For example, such compounds have been shown walls and the like. These waxes and polishes, when apto retain their thixotropic properties in aqueous solutions plied to the surfaces to be treated, prevent the accumulaof 10% sodium chloride, 10% calcium chloride and 5% tion of dust, dirt, grime, etc. which would otherwise ocsodium sulfate. our as the result of static electricity on such surfaces. The following example of a white, indoor, water-base Furthermore, these compounds are substantive to all of paint illustrates the thixotrop-ic properties of the above the aforementioned materials while their compata-bility type compound: with polymeric substances such as epoxy resins, phenolics, compomnt2 Parts by wt. acrylates, cellulose esters, polyolefins, polyurethanes, Behenyl trimethyl ammonium phthalimide polyvmyls, nylon, etc. make them ideal for blending, 1m-

1 5% Solution in 0 100 pregnafilng 90911118 W (a Sodium Salt of a condensed aryl Obviously many modifications and vari ations of the sulfonic acid; produced by Rohm & Haas CO" present invention are possible in the light of the above Philadelphia, Pa) in 25% aqueous S01u teachings. It is, therefore, to be understood that within tion 5 the scope of the :appended claims, the invention may be (produced by Colloids Inc New practiced otherwise than as specifically described.

ark, N1) 3 The invention claimed is Ethylene glycol 20 1. method of inhibiting the growth of m cro- Titanox (titaniam dioxide pigment; organ sms wh ch comprises applying to said microproduced by Titanium Pigment Corp., organisms a biocidally effective amount of a quaternary of Nam Lead CO. New York NY) 220 ammon um aromatic cyclic imide wherein the quaternary Snowflake (a diatomaceous earth produced ammomum canon has the formula:

by Johns-Manville Corp., New York, NY.) 75 a Celite 281 (a di-atornaceous earth produced by Johns-Manville Corp., New York, NY. 50 ib lf dl+ Carbitol 16 c Igepol C0-630 (100% nonyl phenoxy polyoxyethylene ethanol produced by General wherein a and b are members of the group consisting of Aniline and Film Corp., New York, NY.) 3 alkyl and cyclic constituents of pyridinium, isoquino- Water 250 linium, picolinium, imidazolin-ium and morpholini'um, c Polyvinyl acetate (water emulsion having 50% is a member of the group consisting of y y solids) 345 ary'l and cyclic constituents of pyridinium, isoquinolinium A.S.P.-400 (a clay produced by Minerals & and picolinium, 0, when it is a cyclic constituent, being Chemicals Corp. of America, Metuchen, a member of the same ring as a and b, and d is a mem- N.J.) 75 her of the group consisting of alkyl and alkyllaryl, and

wherein the aromatic cyclic imide anion is a member of the group consisting of phthalimide, naphthalimide, benzoxazolinone and benzothiazolinone, the aromatic portion of said anion being substituted by a member of the group consisting of hydrogen, halide, lower alkyl and lower al-koxy, there being a direct electro-valent linkage between the quaternary ammonium cation and the aromatic cyclic imide :anion.

2. A method of inhibiting the growth of microorganisms which comprises applying to said microorganisms a biocid'ally effective amount of a quaternary ammonium aromatic cyclic imide-halogen complex wherein the quaternary ammonium aromatic cyclic imide consists of a quaternary ammonium cation having the formula:

[b-II Td]+ C wherein a and b are members of the group consisting of alkyl and cyclic constituents of pyn'dinium, isoquinolinium, picolinium, imidazolinium and morpholiniurn, c is a member of the group consisting of alkyl, alkylaryl, aryl and cyclic constituents of pyridinium, isoquinolinium and picolinium, c, when it is a cyclic constituent, being a member of the same ring as a and b, and d is a member of the group consisting of alkyl and ralkylaryl, and wherein the aromatic cyclic imide anion is a member of the group consisting of phthalimide, naphthalirnide, benzoxazoli none and benzothiazolinone, the aromatic portion of said anion being substituted by a member of the group consisting of hydrogen, halide, lower alkyl and lower alkoxy, there being a direct electro-valent linkage between the quaternary ammonium cation and the aromatic cyclic imide anion.

References Cited by the Examiner UNITED STATES PATENTS 2,338,516 1/1944 Kern et a1. 2,679,533 5/1954 Darragh et al 16730 X 2,725,326 11/1955 Shibe et al 167-33 3,154,468 10/1964 Aichenegg et a1. 16733 LEWIS GOTTS, Primary Examiner.

RICHARD HUFF, Assistant Examiner. 

1. A METHOD OF INHIBITING THE GROWTH OF MICRORGANISMS WHICH COMPRISES APPLYING TO SAID MICROORGANISMS A BIOCIDALLY EFFECTIVE AMOUNT OF A QUATERNARY AMMONIUM AROMATIC CYCLIC IMIDE WHEREIN THE QUATERNARY AMMONIUM CATION HAS THE FORMULA: 